US3528950A - Polyimide polymers - Google Patents

Polyimide polymers Download PDF

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Publication number
US3528950A
US3528950A US650625A US3528950DA US3528950A US 3528950 A US3528950 A US 3528950A US 650625 A US650625 A US 650625A US 3528950D A US3528950D A US 3528950DA US 3528950 A US3528950 A US 3528950A
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Prior art keywords
polyimides
polyimide
diamine
dianhydride
tetracarboxylic dianhydride
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US650625A
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English (en)
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Hyman R Lubowitz
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Northrop Grumman Space and Mission Systems Corp
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TRW Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H17/00—Switches having flexible operating part adapted only for pulling, e.g. cord, chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid

Definitions

  • the polyimides are prepared by heating polyimide prepolymers having specific terminal or end-capping chemical groups which result from coreactimg specific monoanhydrides with mixtures of dianhydrides and diamines. These chemical groups are stable at room and moderately elevated temperatures but become reactive at temperatures of about 200 to 350 C. thereby forming macromolecules.
  • the specific end-capping anhydrides are compounds having the structural formula where R represents hydrogen or a lower alkyl.
  • Polyimide resins are noted for their outstanding physical and chemical properties, particularly their high temperature thermal stability and high temperature strength. Because of these attractive properties, polyimides have found numerous applications in fields of advancing technology where high-strength, high-temperature materials are required. While these outstanding properties render the polyimides attractive for many and specific applications, economic problems have limited the full potential use of polyimides.
  • polyimides are produced by the reaction between a dianhydride and a diamine. Molecular terminal groups are afforded by the addition of a small amount of a monoanhydride to the batch of the initial reactants. Reaction of the starting constituents produces a polyamide-acid by chain extension or polymerization requiring a period of 30 minutes for some varieties to as much as 4 hours for others. When this polyamide-acid formation has been completed, the material must be kept in solution, hermetically sealed and refrigerated if application is not anticipated within a few hours. Thus, special packaging for subsequent storage is an expense which is passed on to future users. When employed in the final product, the polyamide-acid must be cured by a heat treatment for a period of 5 to 16 hours at elevated temperatures to produce the polyimide which is accompanied by the evolution of an appreciable amount of volatile matter.
  • Preparation of the polyimide prepolymer is effected by dissolving a polyfunctional amine, a polytunctional anhydride, and a monoanhydride as previously described in a solvent, and the solution is refluxed for a period of around 1 8 hours. During the reflux period, a solid primary fraction which is a high molecular weight polyimide separates. At the end of the refluxing period, the solution is cooled to room temperature and the solid primary fraction is separated from the mother liquor and dried. The mother liquor is then treated with an excess of a miscible non-solvent such as water, to coagulate a solid secondary fraction. Removal and drying of the solid secondary fraction is performed in the same way as with the primary fraction.
  • a miscible non-solvent such as water
  • polyimide prepolymers have the following structure where R represents hydrogen or a lower alkyl group and R and R represent an aliphatic or aromatic hydrocarbon group. Because the polyimide prepolymers are a sufficient and stable composition of matter, atmospheric aging is minimized up to temperatures of about 200 C. accordingly, special packaging or storage requirements are not necessary for their protection.
  • Preparation of the polyimides of this invention is accomplished by blending the two polyimide prepolymer powers in pre-determined proportions in the presence or absence of a liquid vehicle. If a vehicle is used, it is preferably driven olT prior to curing the prepolymer. The blended prepolymer is heated to a temperature between 200 to 350 C. whereupon polyimide macromolecules are formed.
  • the polyimides obtained by this process have outstanding thermal and mechanical properties and may be produced from the polyimide prepolymers in a period of 30 minutes or less; in certain cases, post curing of the polyimide may provide improved properties.
  • mixtures containing 100% to by weight of the low molecular Weight polyimide prepolymers may be mixed with the high molecular weight polyimide prepolymer in amounts ranging from 0% to 100% by weight of the lfinal mix, disregarding the amount of the solvent used.
  • the purpose of the mixture of the two polyimide prepolymer fractions is to provide a homogeneous mass at a fusion temperature below the reaction temperature of the end groups. If fusion does not occur, the final product is merely one of a hard granular powder.
  • the low molecular weight polyimide prepolymer may be used by itself, or in amounts down to the minimum required to provide a fusion matrix for the high molecular weight fraction.
  • any polyfunctional amines which is capable of reacting with a polyfunctional anhydride is a suitable constituent for the prepolymer.
  • Suitable polyfunctional amines include diamines or triamines and, in certain instances, tetraamines. The following list is representative of a few of the polyfunctional amines which may be used to produce the polyimide prepolymer:
  • Triarnines such as 1,3,5 -triaminobenzene 2,4,6-triamino-s-triazine 1,2,3-triaminopropane 4,4,4"-triaminotriphenyl methane 4,4,4"-triaminotriphenylcarbinol when reacted With the reactive monoanhydride produce a polyimide prepolymer which is capable of reacting to produce a very stable complex macromolecule of outstanding physical and thermal properties.
  • Polyfunctional anhydrides employed in the production of the polyimide prepolymer according to this invention are generally dianhydrides although triand tetraanhydrides come within the scope of this invention.
  • Polyfunctional anhydrides which have been found to be suitable in the practice of this invention may be selected from the following list which is representative of a few of the anhydrides:
  • pyromellitic dianhydride benzophenone tetracarboxylic dianhydride 2,3,6,7-naphthalene tetracarboxylic dianhydride 3,3,4,4-diphenyl tetracarboxylic dianhydride 1,2,5 ,6-naphthalene tetracarboxylic dianhydride 2,2,3,3'-diphenyl tetracarboxylic dianhydride 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride 3,4,9,l0perylene tetracarboxylic dianhydride bis(3,4-dicarboxyphenyl)ether dianhydride ethylene tetracarboxylic dianhydride naphthalene-1,2,4,5-tetracarboxylic dianhydride naphthalene-1,4,5,8-tetracarboxylic dianhydride decahydronaphthalene-l,4,5,8-tetracar
  • the aromatic chain-terminating agent, or end-capping agent which is used in this invention may be selected from any of the compounds having the structural formula C a r may be selected from any of several polar organic solvents.
  • these solvents are tetramethylurea; dimethylsulfoxide; 1-methy1-2-pyrrolidione; pyridine; dimethylsulfone; hexamethylphosphoramide; N,N-dirnethylformamide; N,N-dimethyl acetamide; tetramethylenesulfone; dimethyltetrarnethylenesulfone; and, in general, any polar organic solvent which does not react with the polyfunctional amines or polyfunctional anhydrides at the process conditions.
  • Non-polar solvents may be employed in conjunction with the above polar solvents as an aid in entraining the prepolymer reaction by-products, principally water.
  • EXAMPLE 1 Approximately 40.7 g. of 4,4'-methylenedianiline, 32.8 g. of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, and 33.9 g. of 3,3',4,4-benzophenone tetracarboxylic acid dianhydride were dissolved in 170 ml. dimethyliormamide and 400 ml. toluene. The solution was refluxed for 18 hours during which time water was collected by means of the Dean Stark receiver. During this reflux period, a cloudy solid phase formed in the solution. At the end of the refluxing period, the solution was cooled to room temperature and filtered. A precipitate or insoluble fraction was collected and dried overnight at 110 C. under vacuum.
  • the filtrate was slowly poured into three liters of rapidly stirring water, and stirring was continued overnight. During the stirring, a second precipitate formed and was collected by filtration and dried overnight at 110 C. under vacuum. The first and second dried precipitates were separately ground into a fine powder with a mortor and pestle. Yields for the first and second precipitates were 32.9 g. and 60.9 g., respectively.
  • the light yellow second fraction was determined to melt between 158 to 180 C.
  • One g. of the second fraction and one g. of the first fraction were mechanically mixed and placed in a 50 ml. beaker.
  • the beaker containing the powder was placed in an oven at 350 C. for 30 minutes and then cooled to room temperature.
  • the resulting polymer was a brown foam.
  • Thermogravimetric analysis showed the polymer to be stabled to 400" C. under nitrogen and had a char residue of 58.9% at 800 C. The char residue was glossy black and maintained the original shape of the sample with slightly
  • EXAMPLE II A solution was prepared by mixing 1000 ml. dimethylformamide and 100 ml. toluene to which 122.7 g. 4,4- oxydianiline was added. The solution was stirred until all the diamine was in solution, and 98.4 g. of 3,6-endomethylene-l,2,3,6-tetrahydrophthalic anhydride was added slowly and stirred until dissolved. Approximately 100.8 g. of 3,3,4,4-benzophenone tetracarboxylic acid dianhydride was added to the solution, and the solution was refluxed for 18 hours, during which time water was collected by means of a Dean Stark receiver. At the end of the refluxing period, the solution was cooled to room temperature and filtered.
  • a precipitate was collected and dried overnight at 110 C. under vacuum.
  • the filtrate was slowly poured into liters of rapidly stirring water and stirred overnight.
  • a second precipitate was collected by filtration and dried overnight at 110 C. under vacuum.
  • the first and second precipitates were separately ground into a fine powder with a mortor and pestle. Yields for the first and second precipitates were 208.0 g. (M.P. 270-280 C.) and 97.7 g. (M.P. l65l90 C.), respectively.
  • One gram of the first precipitate was mechanically mixed with one gram of the second precipitate and heated for 30 minutes at 350 C. The resulting polymer was a dark brown, rigid form.
  • EXAMPLE III Approximately 87.0 g. of 4,4'-oxydianiline were dissolved in a solvent mixture of 700 ml. dimethylformamide and 700 ml. toluene. To this solution is added 65.6 g. of 3,6 endomethylene 1,2,3,6-tetrahydrophthalic anhydride and 63.0 g. of 1,4,5,8-naphthalenetetracarboxylic-1,824,5-
  • the first and second precipitates were separately ground to a fine powder. Yields for the first and second precipitates were 64.0 g. (M.P. 300 C.) and 134.3 g. (M.P. 205-250 C.), respectively.
  • One gram of the first precipitate was mixed with one gram of the second precipitate and placed in a beaker. The beaker containing the powder was then placed -in an oven at 350 C. for 30 minutes and then cooled to room temperature. The resulting black, foam-like polymer tenaciously adhered to the glass.
  • Polyimides obtained by reacting approximately stoichiometric amounts of at least one polyfunctional amine, polyfunctional anhydrides and a monoanhydride characterized by the formula:
  • R is selected from the group consisting of hydrogen and lower alkyl radicals having 1 to 5 carbon atoms. 2.
  • the polyimides of claim 1 further characterized in that R is hydrogen.
  • the polyimides of claim 1 further characterized in that R is a lower alkyl radical.
  • the polyimides of claim 1 further characterized as being cured polyimides having an average molecular weight of at least 10,000.
  • polyimides of claim 1 further characterized in that the polyfunctional amines are diamines and the polyfunctional anhydrides are dianhydrides.
  • a process for preparing polyimides which comprises reacting with the application of heat approximately stoichiometric amounts of at least one polyfunctional amine, polyfunctional anhydrides, and a monoanhydride characterized by the formula:
  • R is selected from the group consisting of hydrogen and lower alkyl radicals having 1 to 5 carbon atoms.
  • cured polyimides are obtained by heating the polyimides at a temperature ranging from about 200 C. to 350 C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
US650625A 1967-07-03 1967-07-03 Polyimide polymers Expired - Lifetime US3528950A (en)

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US65062567A 1967-07-03 1967-07-03

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US (1) US3528950A (en, 2012)
CA (1) CA966250A (en, 2012)
DE (1) DE1770784C3 (en, 2012)
FR (1) FR1572798A (en, 2012)
GB (1) GB1241445A (en, 2012)
NL (2) NL141911B (en, 2012)

Cited By (63)

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US3632428A (en) * 1967-11-30 1972-01-04 Trw Inc Thermally stable coatings
US3708370A (en) * 1971-08-06 1973-01-02 Trw Inc Process for bonding surfaces with polyimide prepolymers
US3708459A (en) * 1970-06-24 1973-01-02 Trw Inc Molding power prepolymers
DE2657128A1 (de) * 1975-12-19 1977-06-23 Ciba Geigy Ag Vernetzbare bis-imidylderivate
DE2657049A1 (de) * 1975-12-19 1977-06-23 Ciba Geigy Ag Vernetzbare tetra-imidylderivate
US4046748A (en) * 1976-04-19 1977-09-06 Arizona Chemical Company Polymers of terpene-maleic anhydride adducts with aliphatic diamines
US4110294A (en) * 1974-04-08 1978-08-29 Ciba-Geigy Corporation Processing aids for high temperature polymers
US4158662A (en) * 1976-12-14 1979-06-19 Ciba-Geigy Corporation Phthalimides substituted by alkenylamino groups
WO1981001855A1 (en) * 1979-12-26 1981-07-09 Gen Electric Heat curable polyimides
US4338430A (en) * 1980-04-18 1982-07-06 Celanese Corporation Preparation of polyimide compositions with cyclic peroxyketal catalyst
US4395514A (en) * 1980-04-18 1983-07-26 Celanese Corporation Process for preparing a carbon fiber reinforced composite article which utilizes a polyimide matrix
US4506100A (en) * 1981-08-12 1985-03-19 National Starch And Chemical Corporation Aromatic diamines
US4604319A (en) * 1984-06-01 1986-08-05 American Cyanamid Company Thermoplastic interleafed resin matrix composites with improved impact strength and toughness
US4647616A (en) * 1985-07-15 1987-03-03 The Dow Chemical Company Thermosettable polymer or prepolymer prepared from herterocycle material containing a nitrogen atom and carboxylic acid mono- or dianhydride
US4654414A (en) * 1985-07-15 1987-03-31 The Dow Chemical Company Thermosettable polymer or prepolymer prepared from heterocyclic material having alkyl substituent, mono- or dianhydride, ethylenically unsaturated material and a hydroxide, carbonate or bicarbonate of a metal of groups I-A or II-A
US4752636A (en) * 1985-07-15 1988-06-21 The Dow Chemical Company Thermosettable polymer or prepolymer prepared from heterocyclic materials containing nitrogen atoms, carboxylic acid mono- or dianhydrides and a polymerizable material with ethylenically unsaturated groups and cured products therefrom
US4778859A (en) * 1985-04-27 1988-10-18 Asahi Kasei Kogyo Kabushiki Kaisha Tetramine derived polyimide with pendant unsaturation, and various photosensitive compositions therefrom
US4818584A (en) * 1987-12-03 1989-04-04 General Dynamics Corp. Arresting delamination in composite laminate
US4847355A (en) * 1985-07-15 1989-07-11 The Dow Chemical Company Thermosettable prepolymer prepared from heterocyclic material having alkyl substituents, mono- or dianhydride, ethylenically unsaturated material and a hydroxide, carbonate of bicarbonate of a metal of groups I-A or II-A
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EP0407825A1 (de) * 1989-07-12 1991-01-16 Bayer Ag Mischungen aus Polyarylensulfiden, Glasfasern und Imiden oder Amidsäuren aus bicyclischen, ungesättigten Disäuren
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US5025084A (en) * 1989-07-15 1991-06-18 Ciba-Geigy Corporation Polyimide-forming compositions
US5041520A (en) * 1988-07-05 1991-08-20 Mitsui Toatsu Chemicals, Inc. Process for preparing polyimide having excellent high temperature stability
US5077382A (en) * 1989-10-26 1991-12-31 Occidental Chemical Corporation Copolyimide odpa/bpda/4,4'-oda or p-pda
US5109105A (en) * 1987-06-12 1992-04-28 The Boeing Company Polyamide oligomers
US5116935A (en) * 1987-05-04 1992-05-26 The Boeing Company Polyimide oligomers and blends and method of curing
US5126085A (en) * 1990-12-07 1992-06-30 Dexter Composites, Inc. Process for preparing polyimide sheet molding compound
US5141804A (en) * 1988-11-01 1992-08-25 American Cyanamid Company Interleaf layer in fiber reinforced resin laminate composites
US5145943A (en) * 1990-12-17 1992-09-08 Ethyl Corporation Production of particulate amide/imide prepolymers
US5151487A (en) * 1985-09-30 1992-09-29 The Boeing Company Method of preparing a crosslinking oligomer
US5171828A (en) * 1989-10-26 1992-12-15 Occidental Chemical Corporation Copolyimide ODPA/BPDA/4,4'-ODA or P-PDA
US5175234A (en) * 1983-09-27 1992-12-29 The Boeing Company Lightly crosslinked polyimides
US5175241A (en) * 1989-12-28 1992-12-29 The Dexter Corporation Polyimide with reduced anhydride content
US5216117A (en) * 1987-09-03 1993-06-01 The Boeing Company Amideimide blends
US5248760A (en) * 1991-01-25 1993-09-28 Unc At Charlotte Chemically cured low temperature polyimides
US5286811A (en) * 1983-09-27 1994-02-15 The Boeing Company Blended polyimide oligomers and method of curing polyimides
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US5344894A (en) * 1983-09-27 1994-09-06 The Boeing Company Polyimide oligomers and blends
US5367083A (en) * 1987-09-03 1994-11-22 The Boeing Company Extended acid halide capping monomers
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US5412065A (en) * 1993-04-09 1995-05-02 Ciba-Geigy Corporation Polyimide oligomers
US5512676A (en) * 1987-09-03 1996-04-30 The Boeing Company Extended amideimide hub for multidimensional oligomers
US5516876A (en) * 1983-09-27 1996-05-14 The Boeing Company Polyimide oligomers and blends
US5573854A (en) * 1981-11-13 1996-11-12 The Boeing Company Composites made from multidimensional oligomers
US5575955A (en) * 1994-07-22 1996-11-19 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrically conductive polyimide film containing gold (III) ions, composition, and process of making
US5587105A (en) * 1988-03-15 1996-12-24 Sheppard; Clyde H. Methods for making liquid molding compounds using diamines and dicyanates
US5602226A (en) * 1985-04-23 1997-02-11 The Boeing Company Method of making multidimensional polyesters
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US5739256A (en) * 1985-04-23 1998-04-14 The Boeing Company Method for making multidimensional polyester oligomers
US5817744A (en) * 1988-03-14 1998-10-06 The Boeing Company Phenylethynyl capped imides
US5914385A (en) * 1996-10-03 1999-06-22 Mitsubishi Jukogyo Kabushiki Kaisha Polyimide resin composition and method for producing prepreg and paint and method for curing resin using the same
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US10442894B2 (en) * 2016-04-01 2019-10-15 Industry-Academic Cooperation Foundation, Yonsei University Microporous polyimide sponge and method for producing the same

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Cited By (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632428A (en) * 1967-11-30 1972-01-04 Trw Inc Thermally stable coatings
US3708459A (en) * 1970-06-24 1973-01-02 Trw Inc Molding power prepolymers
US3708370A (en) * 1971-08-06 1973-01-02 Trw Inc Process for bonding surfaces with polyimide prepolymers
US4110294A (en) * 1974-04-08 1978-08-29 Ciba-Geigy Corporation Processing aids for high temperature polymers
US4219481A (en) * 1975-12-19 1980-08-26 Ciba-Geigy Corporation Crosslinkable bis-imidyl derivatives
DE2657049A1 (de) * 1975-12-19 1977-06-23 Ciba Geigy Ag Vernetzbare tetra-imidylderivate
DE2657128A1 (de) * 1975-12-19 1977-06-23 Ciba Geigy Ag Vernetzbare bis-imidylderivate
US4280946A (en) * 1975-12-19 1981-07-28 Ciba-Geigy Corporation Crosslinkable bis-imidyl derivatives
US4365068A (en) * 1975-12-19 1982-12-21 Ciba-Geigy Corporation Crosslinkable bis-imidyl derivatives
US4046748A (en) * 1976-04-19 1977-09-06 Arizona Chemical Company Polymers of terpene-maleic anhydride adducts with aliphatic diamines
US4158662A (en) * 1976-12-14 1979-06-19 Ciba-Geigy Corporation Phthalimides substituted by alkenylamino groups
WO1981001855A1 (en) * 1979-12-26 1981-07-09 Gen Electric Heat curable polyimides
US4302575A (en) * 1979-12-26 1981-11-24 General Electric Company Heat curable polyimides
US4338430A (en) * 1980-04-18 1982-07-06 Celanese Corporation Preparation of polyimide compositions with cyclic peroxyketal catalyst
US4395514A (en) * 1980-04-18 1983-07-26 Celanese Corporation Process for preparing a carbon fiber reinforced composite article which utilizes a polyimide matrix
US4506100A (en) * 1981-08-12 1985-03-19 National Starch And Chemical Corporation Aromatic diamines
US5714566A (en) * 1981-11-13 1998-02-03 The Boeing Company Method for making multiple chemically functional oligomers
US5573854A (en) * 1981-11-13 1996-11-12 The Boeing Company Composites made from multidimensional oligomers
US5175234A (en) * 1983-09-27 1992-12-29 The Boeing Company Lightly crosslinked polyimides
US5286811A (en) * 1983-09-27 1994-02-15 The Boeing Company Blended polyimide oligomers and method of curing polyimides
US5344894A (en) * 1983-09-27 1994-09-06 The Boeing Company Polyimide oligomers and blends
US5455115A (en) * 1983-09-27 1995-10-03 The Boeing Company Post-cure method for polyimide oligomers
US5516876A (en) * 1983-09-27 1996-05-14 The Boeing Company Polyimide oligomers and blends
US4604319A (en) * 1984-06-01 1986-08-05 American Cyanamid Company Thermoplastic interleafed resin matrix composites with improved impact strength and toughness
US6583255B1 (en) 1985-04-23 2003-06-24 The Boeing Company Polyester oligomer
US5618907A (en) * 1985-04-23 1997-04-08 The Boeing Company Thallium catalyzed multidimensional ester oligomers
US5739256A (en) * 1985-04-23 1998-04-14 The Boeing Company Method for making multidimensional polyester oligomers
US5602226A (en) * 1985-04-23 1997-02-11 The Boeing Company Method of making multidimensional polyesters
US4778859A (en) * 1985-04-27 1988-10-18 Asahi Kasei Kogyo Kabushiki Kaisha Tetramine derived polyimide with pendant unsaturation, and various photosensitive compositions therefrom
US4847355A (en) * 1985-07-15 1989-07-11 The Dow Chemical Company Thermosettable prepolymer prepared from heterocyclic material having alkyl substituents, mono- or dianhydride, ethylenically unsaturated material and a hydroxide, carbonate of bicarbonate of a metal of groups I-A or II-A
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NL6809244A (en, 2012) 1969-01-07
GB1241445A (en) 1971-08-04
CA966250A (en) 1975-04-15
FR1572798A (en, 2012) 1969-06-27
DE1770784C3 (de) 1973-11-15
DE1770784A1 (de) 1971-01-21
DE1770784B2 (de) 1973-04-12
NL141911B (nl) 1974-04-16

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